N,N-bis[6-(benzyloxy)hexa-2,4-diyn-1-yl]-4-methylbenzenesulfonamide | 1510816-15-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N,N-bis[6-(benzyloxy)hexa-2,4-diyn-1-yl]-4-methylbenzenesulfonamide
• CAS: 1510816-15-5
• 化学式: C₃₃H₂₉NO₄S
• 分子量: 535.664
• InChiKey: JKOYIDGNMGFPFK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.43
• 重原子数：
  39.0
• 可旋转键数：
  10.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  55.84
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  N,N-bis[6-(benzyloxy)hexa-2,4-diyn-1-yl]-4-methylbenzenesulfonamide 在 dilithium tetrachlorocuprate 作用下， 以 四氢呋喃 为溶剂， 反应 18.0h， 以83%的产率得到5-((benzyloxy)methyl)-4-(3-(benzyloxy)prop-1-yn-1-yl)-6,7-dichloro-2-tosylisoindoline
  参考文献：
  名称：

  Dichlorination of (Hexadehydro-Diels–Alder Generated) Benzynes and a Protocol for Interrogating the Kinetic Order of Bimolecular Aryne Trapping Reactions

  摘要：

  The efficient dichlorination of benzynes prepared by the hexadehydro-Diels-Alder (HDDA) reaction is reported. Cycloisomerization of a triyne substrate in the presence of dilithium tetrachlorocuprate is shown to provide dichlorinated products A by capture of the benzyne intermediate. A general strategy for discerning the kinetic order of an external aryne trapping agent is presented. It merely requires measurement of the competition between bimolecular vs unimolecular trapping events (here, dichlorination vs intramolecular Diels-Alder (IMDA) reaction to give A vs B, respectively) as a function of the concentration of the trapping agent.

  DOI：

  10.1021/ol403258c
• 作为产物：
  描述：

  N,N-二炔丙基-对甲苯磺酰胺 、 1-((3-bromoprop-2-ynyloxy)methyl)benzene 在 哌啶 、 copper(l) chloride 作用下， 反应 1.0h， 以52%的产率得到N,N-bis[6-(benzyloxy)hexa-2,4-diyn-1-yl]-4-methylbenzenesulfonamide
  参考文献：
  名称：

  Dichlorination of (Hexadehydro-Diels–Alder Generated) Benzynes and a Protocol for Interrogating the Kinetic Order of Bimolecular Aryne Trapping Reactions

  摘要：

  The efficient dichlorination of benzynes prepared by the hexadehydro-Diels-Alder (HDDA) reaction is reported. Cycloisomerization of a triyne substrate in the presence of dilithium tetrachlorocuprate is shown to provide dichlorinated products A by capture of the benzyne intermediate. A general strategy for discerning the kinetic order of an external aryne trapping agent is presented. It merely requires measurement of the competition between bimolecular vs unimolecular trapping events (here, dichlorination vs intramolecular Diels-Alder (IMDA) reaction to give A vs B, respectively) as a function of the concentration of the trapping agent.

  DOI：

  10.1021/ol403258c

文献信息

• Hydroarylation of Arynes Catalyzed by Silver for Biaryl Synthesis
  作者：Nam-Kyu Lee、Sang Young Yun、Phani Mamidipalli、Ryan M. Salzman、Daesung Lee、Tao Zhou、Yuanzhi Xia

  DOI：10.1021/ja500292x

  日期：2014.3.19

  A new biaryl synthesis via silver-catalyzed hydroarylation of arynes from acyclic building blocks with unactivated arenes in intra- and intermolecular manners has been developed. The previously observed Diels-Alder reactions of arynes with arene were not observed under the current silver-catalyzed conditions. Deuterium scrambling and DFT calculations suggest a stepwise electrophilic aromatic substitution

  已经开发了一种新的联芳合成，通过银催化芳烃的加氢芳基化，以分子内和分子间的方式将无环结构单元与未活化的芳烃进行合成。在当前的银催化条件下，未观察到先前观察到的芳烃与芳烃的 Diels-Alder 反应。氘加扰和 DFT 计算表明，通过形成 Wheland 型中间体，然后在加氢芳基化的最后一步中进行水催化的质子转移，这是一种逐步的亲电芳香取代机制。
• Mechanism of the Reactions of Alcohols with <i>o</i>-Benzynes
  作者：Patrick H. Willoughby、Dawen Niu、Tao Wang、Moriana K. Haj、Christopher J. Cramer、Thomas R. Hoye

  DOI：10.1021/ja502595m

  日期：2014.10.1

  determined that (i) it is the carbinol C–H and adjacent O–H hydrogen atoms that are transferred during this process and (ii) the mechanism is consistent with a hydride-like transfer of the C–H. Substrates bearing an internal trap attached to the reactive, HDDA-derived benzyne intermediate were used to probe the kinetic order of the alcohol trapping agent in the H2-transfer as well as in the alcohol addition

  我们研究了仲醇和伯醇与六氢-狄尔斯-阿尔德 (HDDA) 反应生成的苄的反应。这些醇通过竞争加成与二氢转移，分别产生芳醚与还原的苯类产物。在后一过程中，会形成等量的氧化酮（或醛）。使用氘标记研究，我们确定（i）在此过程中转移的是甲醇 C–H 和相邻的 O–H 氢原子，以及（ii）该机制与 C–H 的类氢化物转移一致. 带有连接到反应性 HDDA 衍生的苄中间体的内部陷阱的底物被用于探测醇捕集剂在 H2 转移以及醇添加过程中的动力学顺序。H2-转移反应在酒精中是一级反应。我们的结果暗示了协调一致的 H2 转移过程，这得到了密度泛函理论 (DFT) 计算研究和动力学同位素效应实验结果的进一步支持。相比之下，苯乙炔中的酒精加成是酒精中的二阶，这是一种以前未被认识的现象。额外的 DFT 研究用于进一步探索酒精添加过程的机械方面。